CN104003933A - Preparation method of fluorine group-containing 3-(pyridyl-2-imine)ethyl propionate analogue - Google Patents
Preparation method of fluorine group-containing 3-(pyridyl-2-imine)ethyl propionate analogue Download PDFInfo
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- CN104003933A CN104003933A CN201410202495.6A CN201410202495A CN104003933A CN 104003933 A CN104003933 A CN 104003933A CN 201410202495 A CN201410202495 A CN 201410202495A CN 104003933 A CN104003933 A CN 104003933A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
Abstract
The invention discloses a preparation method of fluorine group-containing 3-(pyridyl-2-imine)ethyl propionate analogue with a structural formula as shown in the description, wherein Rf is 3-F; 4-F; 5-F; 6-F; 3,5-F2; 3-CF3; 4-CF3; 5-CF3; 6-CF3; 3-OCF3; 4-OCF3; 5-OCF3; or 6-OCF3. The preparation method adopts fluorine group-containing 2-aminopyridine analogue and ethyl acrylate as raw materials, carries out a catalytic reaction with Bronsted acid as a catalyst in the absence of solvent or in the presence of an organic solvent, and carries out reduced pressure concentration, silica gel column chromatography separation, and spin drying of the reaction solution to obtain the final product. The preparation method is cheap and easily available in raw materials, low in production cost, simple and environment-friendly in synthetic process, convenient to operate, easy in product separation, and high in yield which is up to 23-60%.
Description
Technical field
The present invention relates to a kind of 3-(pyridyl-2-imines of fluoro-containing group) preparation method of ethyl propionate analogue.
Background technology
Fluorine is a very special element, and many organofluorine compounds also have especially, or even peculiar character.In numerous Drugs Containing Fluorine and polymkeric substance owing to containing fluorine in structure and produced the character of corresponding uniqueness.
From the Composite Logo of fluoro ethyl acetate in 1896 organic fluorine chemistry, along with the enforcement of the Manhattan Project has greatly promoted the development of fluorine chemistry, after this all kinds of fluorochemicalss and polymkeric substance are constantly synthesized.Along with nineteen forty-three has been found the hypertoxic character of single ethyl fluoroacetate, thereby start the research of fluorinated organic compound physiologically active.As a vitochemical subdiscipline, the research of organic fluorine chemistry is in the last few years very active, development also suitable rapidly.
Along with the development of selectivity novel agent and new synthetic method, large quantities of Drugs Containing Fluorines occur in succession, have created surprising social benefit and economic benefit.Because the fluorochemicals that occurring in nature is natural is very rare, thereby to optionally introduce contain fluorine atoms in organic molecule or fluoro-containing group is the very interested research fields of organic fluorine chemistry men to synthesize fluorinated organic compound always.Fluoridize scholar's continuous research through several generations, develop and many contain fluorine atoms has been introduced to the method in organic compound, can be divided on the whole two classes: a class is direct fluorination method, utilize nucleophilic or electrophilic fluorination reagent directly to introduce contain fluorine atoms or fluoro-containing group to organic compound.Another kind of is fluoro-building block method, prepares some fluoro-containing intermediates, using them as fluoro-building block, thereby utilizes original functional group on fluoro-building block to be optionally combined the fluorochemicals of synthetic ad hoc structure with other molecules.Because fluoro-building block method does not relate to the fracture of C-F key, thus it to have selectivity good, reaction temperature and, the advantage that productive rate is higher.
In Chinese patent CN 1861596 A in 2006, be mentioned to the similar synthetic method of involved Compound Phase in a kind of and the present invention, seen following formula:
2007 American Chemical Society's magazine (J. Agric. Food Chem.2007,55,5,416 5422) in weedicide metamifop is reported, mentioned the similar synthetic method of Compound Phase involved in a kind of and the present invention, see following formula:
US Patent No. 20130129677 A1 have also been mentioned to the similar synthetic method of involved Compound Phase in a kind of and the present invention, see following formula:
Only have at present the bibliographical information of above-mentioned similar compound, and involved in the present invention to 3-(pyridyl-2-imines of fluoro-containing group) preparation method of ethyl propionate analogue has no bibliographical information.
Summary of the invention
The object of the invention is the 3-(pyridyl-2-imines for a kind of fluoro-containing group is provided) preparation method of ethyl propionate analogue, the method is used bronsted acid for catalyzer in preparation process, thereby efficient, optionally synthetic a series of fluoro-building block, and the productive rate of final product is higher, productive rate can reach 23-60%.
Technical scheme of the present invention
3-(pyridyl-2-imines of fluoro-containing group) preparation method of analogue of ethyl propionate, 3-(pyridyl-2-imines of described fluoro-containing group) structural formula of ethyl propionate analogue is as follows:
Wherein R
ffor 3-F, 4-F, 5-F, 6-F, 3,5-F
2, 3-CF
3, 4-CF
3, 5-CF
3, 6-CF
3, 3-OCF
3, 4-OCF
3, 5-OCF
3or 6-OCF
3;
Its preparation method is taking the PA analogue of fluoro-containing group and ethyl propenoate as raw material, under solvent-free or organic solvent, taking bronsted acid as catalyzer, the method control temperature heating by direct oil bath is 80-120 DEG C and carries out catalyzed reaction 12-48h, the reaction solution of gained is 40-45 DEG C in temperature, pressure is under 0.09-0.1MPa, to carry out concentrating under reduced pressure, concentrated solution is equipped with sherwood oil through silicagel column: the elutriant that methylene dichloride ratio is 5:1 to 2:1 carries out after column chromatography, elutriant while collecting 2:1, concentrating under reduced pressure obtains 3-(pyridyl-2-imines of fluoro-containing group) analogue of ethyl propionate.
The equation of above-mentioned catalytic reaction process is as follows;
The amount of PA analogue, ethyl propenoate and the catalyzer of above-mentioned catalyzed reaction raw material fluoro-containing group used, calculates the i.e. PA analogue of fluoro-containing group: ethyl propenoate: bronsted acid is 1:1 ~ 4:0.05 ~ 0.5 in molar ratio;
The PA analogue of described fluoro-containing group is 2-amino-5-fluorine pyridine, 2-amino-5-(trifluoromethyl) pyridine or 2-amino-5-(trifluoromethoxy) pyridine;
Bronsted acid used is trifluoroacetic acid, fluoroboric acid, perchloric acid, tosic acid or trifluoromethanesulfonic acid etc., preferably trifluoromethanesulfonic acid;
Organic solvent used is dioxane, toluene or dimethylbenzene etc., preferably toluene;
What described silicagel column used is 100～400 object silica gel.
Beneficial effect of the present invention
3-(pyridyl-2-imines of a kind of fluoro-containing group of the present invention) preparation method of ethyl propionate analogue, owing to directly adopting the PA analogue, ethyl propenoate of fluoro-containing group as raw material, adopting bronsted acid is catalyzer, 3-(pyridyl-2-imines of one-step synthesis fluoro-containing group) ethyl propionate analogue, therefore there is building-up process simple, easy and simple to handle, the features such as the easy separation of product.
Further, 3-(pyridyl-2-imines of a series of fluoro-containing group of the present invention) preparation method of ethyl propionate, the productive rate of final product is high, and its productive rate can reach 23-60%.
Embodiment
Below by specific embodiment, the present invention is further set forth, but do not limit the present invention.
The present invention's raw material, reagent used is commercially available AR, CP level.
The present invention's melting point apparatus used is WRS-2A numeral melting point instrument.
The nuclear magnetic resonance spectrometer that the present invention is used, Avance III 500M, Bruker company of Switzerland produces.
embodiment 1
A preparation method for 3-(pyridyl-2-imines) the ethyl propionate analogue of fluoro-containing group, the structural formula of 3-(pyridyl-2-imines) the ethyl propionate analogue of described fluoro-containing group is as follows:
，
Wherein R
ffor 5-CF
3;
Its preparation method concrete steps are as follows:
In 25mL round-bottomed flask or 15mL tube sealing, add 2-amino-5-(trifluoromethyl) pyridine (500mg, 3.1mmol) and ethyl propenoate (310mg, 3.1mmol), do at toluene under the condition of solvent, with trifluoromethanesulfonic acid (24mg, 0.16mmol) be catalyzer, controlling temperature is at 100 DEG C, to carry out catalyzed reaction 36h.The reaction solution of gained is 40-50 DEG C in temperature, pressure is under 0.09-0.1MPa, to carry out concentrating under reduced pressure, concentrated solution carries out taking sherwood oil: ethyl acetate=10:1 ~ 5:1 as elutriant after column chromatography through silicagel column, elutriant while collecting 5:1, concentrating under reduced pressure obtains faint yellow solid, its productive rate is 23%, m.p.:42.7 ~ 43.4 DEG C;
Raw material 2-amino-5-(trifluoromethyl that above-mentioned catalyzed reaction is used) amount of pyridine, ethyl propenoate and catalyzer, calculate in molar ratio i.e. 2-amino-5-(trifluoromethyl) and pyridine: ethyl propenoate: bronsted acid is 1:1:0.05.
The faint yellow solid product of above-mentioned gained is through nucleus magnetic resonance qualification, and result is as follows:
1h NMR (500 MHz, CDCl
3) δ 8.34 (s, 1H), 7.58 (dd,
j=8.8,2.0 Hz, 1H), 6.45 (d,
j=8.8 Hz, 1H), 5.39 (s, 1H), 4.18 (q,
j=7.1 Hz, 2H), 3.72 (q,
j=6.1 Hz, 2H), 2.66 (t,
j=6.1 Hz, 2H), 1.28 (t,
j=7.1 Hz, 3H), the faint yellow solid that shows thus gained is 3-(5-(trifluoromethyl) pyridyl-2-imines) ethyl propionate.
Above-mentioned is R in structural formula
ffor 5-CF
3a kind of synthetic method of analogue of 3-(pyridyl-2-imines) ethyl propionate of fluoro-containing group, those skilled in the art can select the R in corresponding substrate composite structure formula according to the existing technique means in this area and in conjunction with the above embodiments 1
ffor 3-CF
3, 4-CF
3or 6-CF
3a kind of analogue of 3-(pyridyl-2-imines) ethyl propionate of fluoro-containing group.
embodiment 2
A preparation method for 3-(pyridyl-2-imines) the ethyl propionate analogue of fluoro-containing group, the structural formula of 3-(pyridyl-2-imines) the ethyl propionate analogue of described fluoro-containing group is as follows:
，
Wherein R
ffor 5-F;
Its preparation method specifically comprises the following steps:
In 25mL round-bottomed flask, add respectively 2-amino-5-fluorine pyridine (5.61g, 50mmol) and ethyl propenoate (5.0g, 50mmol), under solvent-free condition, with trifluoromethanesulfonic acid (0.38g, 2.5mmol) be catalyzer, controlling temperature is at 120 DEG C, to carry out catalyzed reaction 12h, the reaction solution of gained is 40-50 DEG C in temperature, pressure is under 0.09-0.1MPa, to carry out concentrating under reduced pressure, concentrated solution carries out taking sherwood oil: ethyl acetate=15:1 ~ 10:1 as elutriant after column chromatography through silicagel column, elutriant while collecting 10:1 respectively, the red liquid that concentrating under reduced pressure obtains, its productive rate is 60%,
The amount of above-mentioned catalyzed reaction raw material 2-amino-5-fluorine pyridine, ethyl propenoate and catalyzer used, calculates i.e. 2-amino-5-fluorine pyridine: ethyl propenoate: bronsted acid is 1:1:0.05 in molar ratio.
The red liquid product of above-mentioned gained is through nucleus magnetic resonance qualification, and result is as follows:
1h NMR (500 MHz, CDCl
3) δ 7.82 (dd,
j=8.1,3.0Hz, 1H), 7.15 (td,
j=8.8,2.0,7.1 Hz, 1H), 6.68 (q,
j=8.8 Hz, 1H), 5.39 (s, 1H), 4.18 (q,
j=7.1 Hz, 2H), 3.72 (q,
j=6.1 Hz, 2H), 2.66 (t,
j=6.1 Hz, 2H), 1.28 (t,
j=7.1 Hz, 3H), the red liquid that shows thus gained is 3-(5-fluorine pyridyl-2-imines) ethyl propionate.
Above-claimed cpd is the R in structural formula
ffor the synthetic method of the analogue of 3-(pyridyl-2-imines) ethyl propionate of a kind of fluoro-containing group of 5-F, those skilled in the art, according to the existing technique means in this area and in conjunction with the above embodiments 2, can select corresponding substrate to synthesize the R in structural formula
ffor 3-F, 4-F, 6-F or 3,5-F
2a kind of analogue of 3-(pyridyl-2-imines) ethyl propionate of fluoro-containing group.
embodiment 3
A preparation method for 3-(pyridyl-2-imines) the ethyl propionate analogue of fluoro-containing group, the structural formula of 3-(pyridyl-2-imines) the ethyl propionate analogue of described fluoro-containing group is as follows:
，
Wherein R
ffor 5-OCF
3;
Its preparation method specifically comprises the following steps:
In 25mL round-bottomed flask, add respectively 2-amino-5-(trifluoromethoxy) pyridine (8.91g, 50mmol) and ethyl propenoate (5.0g, 50mmol), under solvent-free condition, with trifluoromethanesulfonic acid (0.375g, 2.5mmol) be catalyzer, controlling temperature is at 120 DEG C, to carry out catalyzed reaction 24h, the reaction solution of gained is 40-50 DEG C in temperature, pressure is under 0.09-0.1MPa, to carry out concentrating under reduced pressure, concentrated solution carries out taking sherwood oil: ethyl acetate=15:1 ~ 10:1 as elutriant after column chromatography through silicagel column, elutriant while collecting 10:1 respectively, concentrating under reduced pressure obtains yellow-green colour oily matter, its productive rate is 30%,
Raw material 2-amino-5-(trifluoromethoxy that above-mentioned catalyzed reaction is used) amount of pyridine, ethyl propenoate and catalyzer, calculate in molar ratio i.e. 2-amino-5-(trifluoromethoxy) and pyridine: ethyl propenoate: bronsted acid is 1:1:0.05.
The yellow-green colour oily matter product of above-mentioned gained is through nucleus magnetic resonance qualification, and result is as follows:
1h NMR (500 MHz, CDCl
3) δ 7.71 (d,
j=9.0Hz, 1H), 6.98 (dd,
j=8.8,2.0Hz, 1H), 6.68 (q,
j=8.8 Hz, 1H), 5.39 (s, 1H), 4.18 (q,
j=7.1 Hz, 2H), 3.72 (q,
j=6.1 Hz, 2H), 2.66 (t,
j=6.1 Hz, 2H), 1.28 (t,
j=7.1 Hz, 3H), the yellow-green colour oily matter that shows thus gained is 3-(5-(trifluoromethoxy) pyridyl-2-imines) ethyl propionate.
Above-claimed cpd is with the R in structural formula
ffor 5-OCF
3a kind of synthetic method of analogue of 3-(pyridyl-2-imines) ethyl propionate of fluoro-containing group, those skilled in the art, according to the existing technique means in this area and in conjunction with the above embodiments 3, can select corresponding substrate to synthesize the R in structural formula
ffor 3-OCF
3, 4-OCF
3or 6-OCF
3a kind of analogue of 3-(pyridyl-2-imines) ethyl propionate of fluoro-containing group.
In sum, the preparation method of 3-(pyridyl-2-imines) the ethyl propionate analogue of a kind of fluoro-containing group of the present invention, because reaction raw materials is cheap, synthesis step is short, simple to operate, the operating time is shorter, therefore cost is lower, meet industrialization basic demand, the productive rate of final product can reach 23-60%.
Foregoing is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. the 3-(of fluoro-containing group pyridyl-2-imines) preparation method of ethyl propionate analogue, 3-(pyridyl-2-imines of described fluoro-containing group) structural formula of ethyl propionate analogue is as follows:
Wherein R
ffor 3-F, 4-F, 5-F, 6-F, 3,5-F
2, 3-CF
3, 4-CF
3, 5-CF
3, 6-CF
3, 3-OCF
3, 4-OCF
3, 5-OCF
3or 6-OCF
3;
It is characterized in that described preparation method is taking the PA analogue of fluoro-containing group and ethyl propenoate as raw material, under solvent-free or organic solvent, taking bronsted acid as catalyzer, control temperature is 80-120 DEG C and carries out catalyzed reaction 12-48h, the reaction solution of gained is 40-45 DEG C in temperature, pressure is under 0.09-0.1MPa, to carry out concentrating under reduced pressure, concentrated solution is equipped with sherwood oil through silicagel column: the elutriant that methylene dichloride ratio is 5:1 to 2:1 carries out after column chromatography, elutriant while collecting 2:1, concentrating under reduced pressure obtains 3-(pyridyl-2-imines of fluoro-containing group) analogue of ethyl propionate.
2. the 3-(of a kind of fluoro-containing group as claimed in claim 1 pyridyl-2-imines) preparation method of ethyl propionate analogue, it is characterized in that described bronsted acid is trifluoroacetic acid, fluoroboric acid, perchloric acid, tosic acid or trifluoromethanesulfonic acid.
3. the 3-(of a kind of fluoro-containing group as claimed in claim 1 pyridyl-2-imines) preparation method of ethyl propionate analogue, it is characterized in that the amount of PA analogue, ethyl propenoate and the bronsted acid of catalyzer of raw material fluoro-containing group used, calculate in molar ratio the i.e. PA analogue of fluoro-containing group: ethyl propenoate: bronsted acid is 1:1 ~ 4:0.05 ~ 0.5.
4. the 3-(of a kind of fluoro-containing group as claimed in claim 2 pyridyl-2-imines) preparation method of ethyl propionate analogue, it is characterized in that the amount of PA analogue, ethyl propenoate and the bronsted acid of catalyzer of raw material fluoro-containing group used, calculate in molar ratio the i.e. PA analogue of fluoro-containing group: ethyl propenoate: bronsted acid is 1:1:0.05 ~ 0.5.
5. the 3-(of a kind of fluoro-containing group as claimed in claim 4 pyridyl-2-imines) preparation method of ethyl propionate analogue, it is characterized in that described organic solvent is toluene, dimethylbenzene or dioxane.
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2014
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Application publication date: 20140827 |